Processes for breaking petroleum emulsions



Patented Oct. 16, 1951 PROCESSES FOR BREAKING PETROLEUM EMULSIONS MelvinDe Groote, University City, and Bernhard Keiser, Webster Groves, Mo.,assignors to Petrolite Corporation, Ltd., Wilmington, DeL, a corporationof Delaware No Drawing.

Application January 6, 1950, Serial No. 137,291

12 claims. (or. 252-442 This invention relates to processes orprocedures particularly adapted for preventing, breaking, or resolvingemulsions of the water-in-oil type, and particularly petroleumemulsions, the present application being a continuation-in-part of ourco-pending application Serial No. 8,723, filed February 16, 1948, whichhas now matured into Patent No. 2,499,366, dated March 7, 1950.

Complementary to the above aspect of the invention is our companioninvention concerned with the new chemical products or compounds used asthe demulsifying agents in said aforementioned processes or procedures,as well as the application of such chemical compounds, products, and thelike, in various other arts and industries, along with the method formanufacturing said new chemical products or compounds which are ofoutstanding value in demulsification. See our co-pending applicationSerial No. 137,292, filed January 6, 1950.

As will be apparent hereafter, the present invention involves as areactant, a new type of resin prepared from salicylic acid inconjunction with an alkylated phenol and an aldehyde. Such resin is of apeculiar nature, from the standpoint of chemical reactivity, by virtueof the carboxyl radical and is completely soluble in non-polar solventssuch as xylene. Such resin has oilsolubility of an entirely difierentcharacter than that of resins obtained solely from salicylic acid.

This phase of the invention more specifically is described and claimedin our co-pending application Serial No. 137,292, filed January 6, 1950.

Our invention provides an economical and rapid process for resolvingpetroleum emulsions of the water-in-oil type that are commonlyreferredto as cut oil, roily oil, emulsified oil, etc., and which comprise finedroplets of naturally-occurring waters or brines dispersed in a more orless permanent state throughout the oil which con-.. stitutes thecontinuous phase of the emulsion.

It also provides an economical and rapid process for separatingemulsions which have been prepared under controlled conditions frommineral oil, such as crude oil and relatively soft waters or weakbrines. Controlled emulsification and subsequent demulsification, underthe conditions just mentioned, are of significant value in removingimpurities, particularly inorganic salts, from pipeline oil.

Demulsification, as contemplated in the pres-- drocarbon component.

Briefly stated, the present process is concerned with the breaking orresolving of petroleum emulsions by means of the oxyalkylatedderivatives of certain resins hereinafter specified.

Thus, the present process is concerned with breaking petroleum emulsionsof the water-in-oil type, characterized by subjecting the emulsion tothe action of hydrophile hydroxylatedsynthetic products; said hydrophilesynthetic products being oxyalkylation products of (A) An alpha-betaalkylene oxide having not more than 4 carbon atoms and selected from theclass consisting of ethylene oxide, propylene oxide, butylene oxide,glycide and methylglycide; and

(B) An Oxyalkylation-susceptible, fusible, xylene-soluble,water-insoluble, acid-catalyzed, lowstage, phenol-aldehyde resin; saidresin being derived by reaction between a mixture of a difunctionalmonohydric hydrocarbon-substituted phenol and salicylic acid on the onehand, and an aldehyde having not Over 8 carbon atoms and reactivetowards both components of the mixture on the other hand; the amount ofsalicylic acid employed in relation to the nOn-carboxylated phenol beingsufilcient to contribute at least one salicylic acid radical per resinmolecule; said resin being formed in substantial absence oftrifunctional phenols, and said phenol being of the formula W in which Ris a hydrocarbon radical having at least 4 and not more than 14 carbonatomsand substituted in the 2,4,6 position; said oxyalkylated resinbeing characterized by the introduction into the resin molecule of aplurality of divalent radicals having the formula (R1O),u in which R1 isa member selected from the class consisting of ethylene radicals,propylene radicals, butylene radicals, hydroxypropylene radicals, andhydroxy' butylene radicals, and n is a numeral varying from 1 to 30,with the proviso that at least 2 moles of alklene oxide be introducedfor each phenolic nucleus.

As has been pointed out previously, one phase of the invention isconcerned with the preparation of resins from salicylic acid and adifunctional, monohydric, hydrocarbon substituted phenol, or phenols. Inother words, there must be at least one difunctional phenol, such asbutyl phenol, amyl phenol, hexyl phenol, octyl phenol, decyl phenol,dodecyl phenol, and salicyclic acid, but one may employ a mixture, forinstance, one mole of amyl phenol and one or more moles of butyl phenol;in combination with salicylic acid;

or one mole of octylphenol and one or more moles of nonyl phenol, incombination with salicylic acid; or one mole of decyl phenol and one ormore moles of dodecyl phenol, in combination with salicylic acid.

To avoid awkward and cumbersome terminology which may be confusing,reference in this application and in the claims to a difunctional,monohydric, hydrocarbon-substituted phenol and salicyclic acid orequivalent language does not mean that one must use a single phenol,but,

as pointed out, a mixture of such phenols is equally satisfactory.Similarly, the expression noncarboxylated phenol, unless otherwisequalified, includes either a single non-carboxylated phenol, or amixture of one or more non-carboxylated phenols. v

Reference has been made to salicylic acid. The other isomer, parahydroxybenzoic acid would, of course, serve just as satisfactorily as salicylicacid, but it happens that para-hydroxy benzoic axid sells at severaltimes as much per pound and seems to yield compounds which are of noincreased value. For this reason reference is made to salicylic acid,but it is obvious that the isomeric compound is the functionalequivalent.

For purpose of convenience, what is said hereinafter will be dividedinto three parts:

Part 1 will be concerned with the production of the resin from a mixtureof the kind specified and described in greater detail subsequently:

Part 2 will be concerned with the oxyalkylation of the resin so as toconvert it into a hydrophile hydroxylated derivative; and

Part 3 will be concerned with the use of such derivatives asdemulsifiers, as hereinafter described.

PART 1 The production of resins from difunctionalhydrocarbon-substituted phenols is well known and such resinsareimportant in the art, particularly in the preparation of varnishes orsimilar coatings. The literature contains references to the preparationof salicylic acid resins. These particular resins, as far as we areaware, have not found any utility whatsoever in any industrial field. Weknow of no other utility for the resins derived from the mixture hereindescribed other than what is said in the instant application.

For reasons which become obvious, it is believed it may be well to notethe preparation of a suitable resin from a hydrocarbon-substituteddifunctional monohydric phenol alone, and also a resin made fromsalicylic acid alone.

.Certain advantages in manipulation, etc., will become obvious in regardto such instances where a mixture of reactants is employed, as in the 14carbon atoms.

instant application, insofar as the present invention is concerned.

' Example 1a Grams Para-tertiary butylphenol 150 Formaldehyde 37% 81Concentrated HCl 1.5 Monoalkyl (Cm-C20, principally C12-C14) benzenemonosulfonic acid sodium salt 0.8

Xylene 100 (Examples of alkylaryl sulfonic acids which serve ascatalysts and as emulsifiers, particularly in the form of sodium salts,include the following:

(R is an alkyl hydrocarbon radical having 12-14 carbon atoms.

(R is an alkyl radical having 3-12 carbon atoms and n represents thenumeral 3, 2, or 1, usually 2, in such instances where R contains lessthan 8 carbon atoms.

(With respect to alkylaryl sulfonic acids or the sodium salts, we haveemployed a monoalkylated benzene monosulfonic acid or the sodium saltthereof, wherein the alkyl group contains 10 to We have found equallyeffective and interchangeable the following specific sulfonic acids ortheir sodium salts: A mixture of diand tripropylated naphthalenemonosulfonic acid; diamylated naphthalene monosulfonic acid; and nonylnaphthalene monosulfonic acid.)

The equipment used was a conventional twopiece laboratory resin pot. Thecover part of the equipment had four openings: One for reflux condenser;one for the stirring device; one for a separatory funnel or other meansof adding reactants; and a thermometer well. In the manipulationemployed, the separatory funnel insert for adding reactants was notused. The device was equipped with a combination reflux and water-trapapparatus, so that the single piece of apparatus could be used as eithera reflux condenser or a water trap, depending upon the position of thethree-way glass stopcock. This permitted convenient withdrawal of waterfrom the water trap. The equipment, furthermore, permitted any settingof the valve without disconnecting the equipment. The resin pot washeated with a glass fibre electrical heater constructed to flt snuglyaround the resoin pot. Such heaters, with regulators, are readilyavailable.

The phenol, formaldehyde, acid catalyst, and solvent were combined inthe resin pot above described. This particular phenol was in the form ofa flaked solid. Heat was applied with gentle stirring and thetemperature was raised to -85 'C., at which point a mild exothermicreaction took place. This reaction raised the temperature toapproximately 105-100" C. The reaction mixture was then permitted toreflux at -105 C. for between one and one and one-half hours. The refluxtrap arrangement was then changed from the reflux position to the normalwater entrapment position. The water of solution and the water ofreaction we're permitted to distil out and collect in the trap. As thewater distilled out, the temperature gradually increased toapproximately 150 C. which required between 1.5 to 2 hours. At thispoint the water recovered in the trap, after making allowance for asmall .amount of water held up in the solvent, corre I sponded to theexpected quantity.

The solvent solution so obtained was used as such in subsequentoxyalkylation steps. We have also removed the solvent by conventionalmeans, such as evaporation, distillation or vacuum distillation, and wecustomarily take a small sample of the solvent solution and evaporatethe solvent to note the characteristics of the solvent-free resin. Theresin obtained in the operation above described was clear, light ambercolored, hard, brittle, and had a melting point of 160l65 C.

Attention is directed to the fact that tertiary butylphenol, in presenceof a strong mineral acid asa catalyst and using formaldehyde, sometimesyields a resin which apparently has a very slight amount ,ofcross-linking. Such resin is similar to the one described above, exceptthat it is somewhat opaque, and its melting point is higher than the onedescribed above and there is a tendency to cure. Such a resin isgenerally dispersible in xylene, but not soluble to give a clears)lution. Such dispersion can be oxyalkylated in the same manner as theclear resin. If desired; a minor proportion of another and inertsolvent, such as diethyleneglycol diethylether, may be employed alongwith xylene, to give a clear solution prior to oxyalkylation. This factof solubilization shows the present resin molecules are still quitesmall, as contrasted with the very large size of extensivelycross-linked resin molecules. If, in following a given procedure with agiven lot of 'the phenol,-such a resin is obtained, the amount ofcatalyst employed is advantageously reduced slightly, or the time ofreflux reduced slightly, or both, or an acid such as oxalic acid is usedinstead of hydrochloric acid. Purely as a matter of convenience, due tobetter solubility in xylene, we prefer to use a clear resin, but ifdesired either type may be employed. (See Example 1a of aforementionedco-pending application Serial No. 8,723, filed February 16, 1948.)

Example 2a Grams Salicyclic acid (U. S. P. grade) 50 Formaldehyde 30% 75Water 200 Concentrated HCl 5 The above ingredients were combined in aconventional glass flask with a stirring device and condenser. Themixture was refluxed for 20 hours at a. temperature of approximately 100C., or slightly in excess thereof. At the end of this time thereseparated out an aqueous layer and a resinous layer, and the aqueouslayer was withdrawn. The non-aqueous layer, which was more or less asolid, was heated to 240-25) C., during which time the remainder of thewater present was eliminated. The resultant resin was clear, brittle andhard. It was not xylene-soluble, but was soluble in a mixture consistingof 50% xylene and 50% diethylene glycol diethylether. (See Example 19611of aforementioned co-pending application, Serial No. 8.723. filedFebruary 16 (1948.)

Example 30 Grams Salicyclic acid 150 Hexamethylenetetramine 34 Alcohol(ethyl) 400 The above mixture was refluxed for 20 hours. At the end ofthis time the'mixture was heated to 150 C. with a distillation of allthe alcohol. The resultant product was a dark red hydroscopic resin.This'resin was then dissolved in 600 grams of anhydrous methyl alcohol.and 2 grams of paratoluene sulfonic acid added as a catalyst. Thismixture was then refluxed for 20 hours. At the end of this time thealcohol was removed along with water of esterification. The resin wasdissolved again in another 600 gram lot of methyl alcohol and againrefluxed for 20 hours. At the end of this time the alcohol and waterwere distilled oil again and the resin dissolved for a third time in 600grams of anhydrous methyl alcohol and again refluxed for 20 hours. Atthe end of this period of time the methanol and water formed weredistilled oil, yielding the methyl ester in presence of a small amountof sulfonic acid present as a catalyst.

The resin was dark red in color and very soft. It was not soluble inxylene but 100 grams of resin made a very satisfactory solution with 50parts of xylene and 50 parts of diethylene glycol diethylether. (SeeExample 197a of aforementioned co-pending application Serial No. 8,723,filed February 16, 1948.)

The same procedure was followed as was described under the heading ofExample 1a, except that the initial reflux period was 2 hours instead of1% hours. At the end of this first reflux period there was still astrong odor of formaldehyde present. Two grams more of concentratedhydrochloric acid were added. The mixture was then refluxed for 5% hoursmore, at which time there was still a strong odor of formaldehydepresent in a sample of the aqueous distillate from the reflux condenser.As a result, 10 more grams of hydrochloric acid were added and thereflux procedure continued for a third period of 1'7 hours. During thislast reflux period the trap arrangement was changed so as to permit theaqueous distillate to distil over and be trapped. This distillate stillcarried some odor of formaldehyde and there was also some uncombinedsalicyclic acid remaining in the hot solution; probably more than andpossibly of the reactants, entered into the reaction. ,The salicyclicacid remaining in the reaction mass was filtered out hot. On cooling,the solution became thick and syrupy, but was of suflicient solubilityand viscosity to be suitable for oxyalkylation. (See Example 198a ofaforementioned co-pending application Serial No. 8,723, filed February16, 1948.)

The same procedure was followed as, in Example la, preceding, exceptthat the reflux period was 8 hours. At the end of this time there wasstill a strong odor of formaldehyde present in the vapors, and there waspresent in the flask unreacted salicyclic acid. For this reason, anothermole of formaldehyde was added (81 grams) and the resiniflcation periodrepeated salicyclic acid resin insofar that it began to separate outfrom the xylene solution. For this reason 50 grams of diethylene glycoldiethylether were added and then the mixture distilled so as to remove50 grams of xylene. When this final product was allowed to cool andstand, it

remained clear.

Reference is made to the two types of resins which have been previouslydisclosed, to wit, conventional resins derived from alkylated phenols,which are-xylene-soluble, but do not include in the resin molecule acarboxyl group for reactions of the kind in which the carboxyl radicalis involved, such as esteriflcation, amidiflcation, etc. Likewise, therehas been illustrated the salicylic acid resins which are notparticularly oil-soluble and are not xylene-soluble, but whosesolubility depends on the addition of a more expensive oxygenatedsolvent, such as diethylene glycol diethylether, or an alcohol, which,of course, is oxyalkylation-susceptible.

Therefore, in order to prepare the typeof materials herein described, wehave had to prepare a new reactant, to wit, a resin derived from acombination in which salicylic acid and alkylated.

The value 'of salicylic acid as a resin making compound for theproduction of compounds for use in the present invention, restsnot somuch in the use of the product as such, as in its use in admixture withother phenolic reactants. Thus, if one makes a mixture of approximately4 moles of para-amylphenol, for example, and one mole of salicylic acidand resinifles the mixture, there are two advantages:

(1) The mixture is soluble or, at least, it can be handled in xylenemuch more advantageously than resins from salicylic acid alone; and

(2) One obtains a resin which has certain possibilities for furtherreaction which are not presentin the usual hydrocarbon-substitutedphenol. In its simplest aspect it may be represented in an idealizedform, in the following manner:

OH OH OH OH OH H H H H 1100 C C C C H H H H Amyl Amyl Amy] Amy] Theabove formula is, of course, an idealized structure, for obviousreasons, because the salicylic acid nucleus presumably can appear at anypoint in the resin molecule. Such resin, or for that matter, a resinhaving an increased number of salicylic acid radicals, can beoxyalkylated in the same manner as other phenol-aldehyde resins.

The reactive carboxyl radical permits a number of variations. Thus, theresin can be reacted with reagents such as ethylene glycol, glycerol,triethanolamine, diethanolamine, etc. (See Example 199a ofaforementioned co-pending application, Serial No. 8,723, filed February16, 1948.)

Example 6a Grams Salicylic acid 69 Para-tertiary amylphenol 328Monoalkyl (Cw-C20, principally Cir-C14) benzene monosulfonic acid sodiumsalt Concentrated HCl 20 Xylene 400 Formaldehyde 208 The same procedurewas followed as in Example 1a, except that the amount of hydrochloricacid employed is comparatively high, to wit, 20 grams, and the reflextime, instead of being 1 /2 hours, was 3 hours. Only a very small amountof salicylic acid was lost on evaporation. The resin was soft and tacky,and xylene-soluble. (See Example 20011 of aforementioned co-pendingapplication Serial No. 8,723, flled February 16, 1948.)

Example 7a Para-tertiary amylphenol (4.0 moles) grams 656 Salicylic acid(1.0 mole) do 138 Formaldehyde 37% (5.0 moles) do 405 Xylene do 700 K01(concentrated) milliliters 40 Dodecyl toluene monosulfonic acid sodiumsalt ams 3 Example Para-tertiary nonylphenol (4.0 moles) rams 880Salicylic acid (1.0 mole) do 138 Formaldehyde 37% (5.0 moles) -do 405Xylene do 600 HCl (concentrated) milliliters 40 Dodecyl toluenemonosulfonic acid sodium sa ams" 3 The same procedure'was followed as inExample 1a, preceding, except that the reflux period was 5 hours,instead of 1% hours. Also, note the marked increase in amount of acidused as a catalyst in this instance.

The resin solution, so obtained, contained approximately 38.5% xylene.The solvent-free resin was clear, pale reddish amber in color,xylene-soluble, and soft to semi-pliable in consistency.

ample 1a, preceding, exceptthat the reflux period was 5 hours, insteadof 1% hours. Also, note the marked increase in amount of acid used as acatalyst in this instance.

The resin solution, so obtained, contained approximately 46.6% xylene.The solvent-free resin The same procedure was followed'as in Exentirelysoluble in xylene.

was pale reddish amber in color, slightly opaque, xylene-dispersible,and hard but not brittle in consistency, with a low-melting point.

Example 10a Para secondary butylphenol (4.0

moles) grams 600 Salicylic acid (1.0 mole) do 138 Formaldehyde 37% (5.0moles) do 405 Xylene do 700 Dodecyl toluene monosulfonic acid sodiumsalt ams-.. 3 H01 (concentrated) milliliters 40 The same procedure wasfollowed as in Example 1a, preceding, except that the reflux period was5 hours, instead of 1% hours. Also, note the marked increase in amountof acid used as a catalyst in this instance.

The resin solution, so obtained, contained approximately 46.5% xylene.The solvent-free resin was amber in color, slightly opaque, and almostIt was fairly hard or pliable in consistency.

Example 11a Menthylphenol (4.0 moles) grams 928 Salicylic acid (1.0mole) do 138 Formaldehyde 37% (5.0 moles) do 405 Xylen do 700 E01(concentrated) milliliters 40 Dodecyl toluene monosulfonic acid sodiumsalt rams 3 The same procedure was followed as in Exam ple 1a preceding,except that the reflux period was 5 hours, instead of 1 /2 hours. Also,note the marked increase in amount of acid used as a catalyst in thisinstance.

The resin solution, so obtained, containedapproximately 41.5% xylene.The solvent-free resin was deep red or reddish amber in color, clear,xylene-soluble, and pliable, but not hard in consistency.

Example 12a Para-tertiaryoctylphenol (4.0moles) grams 824 Salicylic acid(1.0 mole) do 138 Formaldehyde 37% (5.0 moles) do 405 Xylene do 650 E01(concentrated) "milliliters" 40 Dodecyl toluene monosulfonic acid sodiumsalt ams" 3 The same procedure was followed as in Example 1a, preceding,except that the reflux period was 5 hours, instead of 1 hours. Also,note the marked increase in amount of acid used as a catalyst in thisinstance.

The resin solution, so obtained, contained approximately 38.8% xylene.The solvent-free resin was reddish amber in color, clear, xylenesolubleand semi-hard to pliable in consistency.

Example 13a Para-tertiaryamylphenol(3.0moles) -grams 492 Salicylic acid(2.0 moles) ..do 276 Formaldehyde 37% (5.0 moles) do 405 Xylene do 700E01 (concentrated) milliliters 40 Dodecyl toluene monosulfonic acidsodium salt rams-" 3 The same procedure was followed as in Example 1a,preceding, except that the reflux period was 5 hours, instead of 1 /2hours. Also, note the marked increase in amount of acid used as acatalyst in this instance.

The resin solution, so obtained, contained anproximately 48.8% xylene.The solvent-free resin was reddish amber in color, clear, xylenesolubleand semi-soft or pliable in consistency.

Example 14a Para-secondary butylphenol (3.0 moles) grams 450 Salicylicacid (2.0 mo1es) do.. 276 Formaldehyde 37% (5.0 moles) "do"-.. 405 HCl(concentrated) milliliters.. 40 xylene erams 700 Dodecyl toluenemonosulfonic acid sodium salt' Prams-.. 3

The same procedure was followed as in Example 1a, preceding, except thatthe reflux period was 5 hours, instead of 1%.; hours. Also, note themarked increase in amount of acid used as a catalyst in this instance.

The resin solution, so obtained, contained approximately 44.2% xylene.The solvent-free resin was amber in color, slightly opaque, almostentirely soluble in xylene, and fairly hard or pliable in consistency.

Example 15a Para-tertiary butylphenol (3.0 moles) grams 450 Salicylicacid (2.0 moles) do 276 Formaldehyde 37% (5.0 moles) do..- 405 HCl(concentrated) milliliters 40 Xylene ams" 700 Dodecyl toluenemonosulfonic acid sodium salt amsm 3 The same procedure was followed asin Example la, preceding, except that the reflux period was 5 hours,instead of 1 hours. Also, note the marked increase in amount of acidused as a catalyst in this instance.

The resin solution contained approximately 44.2% xylene. Thesolvent-free resin was pale reddish amber in color, almost clear, andfairly hard or pliable in consistency.

was 5 hours, instead of 1 /2 hours. Also, note the marked increase inamount of acid used as a catalyst in this instance.

The resin solution, so obtained, contained approximately 42.3% xylene.The solvent-free resin was clear, reddish amber in color, xylenesoluble,and semi-hard to pliable in consistency.

Example 17a Para-menthylphenol (3.0 moles) grams 696 Salicylic acid (2.0moles) do 276 Formaldehyde 37% (5.0 moles) do 405 Xylene do HCl(concentrated) milliliters 40 Dodecyl toluene monosulfonic acid sodiumsalt erams 3 The same procedure was followed as in Example 1a,preceding, except that the reflux period was 5 hours. instead of 1%hours. Also, note the marked increase in amount of acid used as acatalyst in this instance.

The resin solution, so obtained, contained approximately 40.3% xylene.The solvent-free resin was slightly softer in consistency than theresultant in Example 11a, preceding, but it had the same deep red orreddish amber color, and was clear, xylene-soluble and pliable but nothard Example 18a Para-tertiary nonylphenol (3.0 moles) grams 660Salicylic acid (2.0 moles) do 276 Formaldehyde 37% (5.0 moles) do 405Xylene do 700 HCl (concentrated) -milliliters 40 Dodecyl toluenemonosulfonic acid sodium salt grams 3 Example 19a Grams Para-tertiaryamylphenol (4.0 moles) 656 Salicylic acid (1.0 mole) 138 Propionaldehyde(5.0 moles) 305 Xylene 700 Concentrated sulfuric acid 20 Wheneverpropionaldehyde or similar aldehydes were employed the procedure waschanged slightly from that employed in Example 1a. The equipmentemployed, however, was the same. The am lphenol, salicyclic acid, xyleneand acid catalyst were combined in the resin pot, stirred and heated to150 C. At this point the propionaldehyde was added slowly for about 1hours, after which the whole reaction mass was permitted to reflux for 5hours at the reflux temperature of water or slightly above, i. e.,100-110 C., before distilling out water. The amount of water distilledout was 102 cc. Compare this procedure with that employed in Example 24ain Serial No. 8,723, filed February 16, 1948.

The resin solution, so obtained, contained approximately 41.2% xylene.The solvent-free resin was reddish-black, clear, xylene-soluble and hardbut not brittle in consistency.

The procedure followed was the same as that outlined in Example 19a,preceding. The resin solution, so obtained, contained approximately42.6% xylene, and the solvent-free resin was reddish black in color,clear, hard and brittle, xylenesoluble,. and had a melting point ofabout 82 C.

Example 21a Grams Para-secondary butylphenol (4.0 moles).,.. 600Salicylic acid (1.0 mole) 138 Propionaldehyde 96% (5.0 moles) 305Sulfuric acid- 20 Xylene 700 The same precedure was followed as inExample 19a, preceding. The resin solution, so obtained, combinedapproximately 42.6% xylene. The solvent-free resin was reddish black incolor, clear and xylene-soluble. It was fairly hard to semi-pliable inconsistency.

Example 22a Grams Para-octylphenol (4.0 moles) 824 Salicylic acid (1.0mole) 138 Propionaldehyde 96% (5.0 moles) 305 Sulfuric acid- 20 Xylene700 The same procedure was followed as in Example 19a, preceding. Theresin solution, so obtained, contained approximately 37.5% xylene. Thesolvent-free resin was dark amber in color, but clear andxylene-soluble, and hard but not brittle in consistency.

Example 23a Grams Methylphenol (4.0 moles) 928 Salicylic acid (1.0 mole)138 Propionaldehyde 96% (5.0 moles) 305 Sulfuric aoid 20 Xylene 700 Thesame procedure was followed as in Example 19a, preceding. The resinsolution, so obtained, contained about 35.6% xylene. The solvent-freeresin was reddish black and clear, in color; xylene-soluble and fairlyhard to semi-pliable in consistency.

Example 24a Grams Nonylphenol (4.0 moles) 880 Salicylic acid (1.0 mole)138 Propionaldehyde 96% (5.0 moles) 305 Sulfuric acid- 20 Xylene 700 Thesame procedure was followed as in Exammainly of the para-substitutedproduct, usually associated with some of the ortho-substituted product,perhaps a very small proportion of meta-substituted material, someimpurities, etc. Also, it is to be understood that all of the productsof the foregoing examples, unless it is otherwise stated in the example,aresoluble in xylene, at least to an extent sufficient to permit the useof xylene as the solvent in oxyalkylation.

Attention is directed to the use of 0-10 to 0-14 substituted phenols. Wehave found these higher substituted phenols can replace an equivalentamount of the lower substituted phenols in any one of the precedingexamples, using mixtures of salicylic acids, and particularly phenols,in the same molal ratio, for instance, particularly Examples 6a or 7a.In fact, particularly attractive mixed resins are obtained, usingtetradecylphenol. Difunctional tetradecylphenols are available at anattractive price. One grade of. these particular phenols consists of amixture representing about 90% para-substituted phenol,ortho-substituted phenol, and 5% meta-substituted phenol. Although thesame amount of meta-substituent is comparatively large compared withother difunctional phenols, it appears unobjectionable, due to thecomparatively large side chain. For example, compare with thepreparation of soluble thermoplastic phenols from cardanol, or sidechain hydrogenated cardanol. We have prepared resins from such phenolalone, or in admixture following the same procedure described inspecific examples preceding. As a specific example, we have substitutedthis particular tetradecylphenol in Examples 6a, 7a, and 19a. and haveobtained products having similar characteristics, except that, ifanything, the resins were somewhat darker and somewhat more fluid.Similarly, tetradecylphenol can be used with acetylene, in combinationwith the other aldehydes described.

The use of the higher alkylated phenols, particularly decylphenol,dodecylphenol and tetradecylphenol, in the preparation of salicylic acidcontaining resins is, of course, not limited to the use of suchnon-carboxy phenols alone, but one can, of course, make mixtures whichgive excellent results; for instance, one part of salicylic acid, twoparts of para-tertiary amylphenol, and two parts of tetradecylphenolgrade 14-60691 previously described. In a similar mixture the amylphenolcan be replaced by butylphenol, or

octylphenol; likewise, in analogous mixtures the tetradecylphenol couldbe replaced by decylphenol or dodecylphenol. All of this is perfectlyobvious in light of what has been said previously and requires nofurther description.

In the preceding examples the aldehydes used have been formaldehyde andpropionaldehyde. Any aldehyde capable of forming a methylol' or asubstituted methylol group, and having not more than 8 carbon atoms issatisfactory, so long as it does not possess some other functional groupor structure which will conflict with the resinification reaction orwith the subsequent oxyalkylation of the resin, but the use offormaldehyde in its cheapest form of an aqueous solution, for theproduction of the resins, is particularly advantageous. Solid polymersof formaldehyde are more expensive and higher aldehydes are both lessreactive and are more expensive. Furthermore, the higher aldehydes mayundergo other reactions which are not desirable, thus introduc ingdifliculties into the resinification step. Thus acetaldehyde, forexample, may undergo an aldol condensation, and it and most of thehigher aldehydes enter into self-resinification when treated with strongacids or alkalies. On the other hand, higher aldehydes frequentlybeneficially affect the solubility and fusibility of a resin. This isillustrated, for example, by the different characteristics of the resinprepared from para-tertiary amylphenol and formaldehyde on one hand, andI handle in the subsequent oxyalkylation procedure.

found such modification desirable. When an acid catalyst is used, afurfural vinyl condensation is apt to take place. tion of the aldehydeand a catalyst must be com patible with the use of the salicylic acid,and for practical purposes, this seems to limit the method in a largemeasure to acid catalysts, such as those described. As is well known,resins of the kind herein described contain at least three phenolicnuclei. The resins herein described including use of salicylic acid, areusually formed in the presence of a large amount of an acid catalyst.This means that the resin is apt to give more than three nuclei; inother words, an average of 4, 5, 5 or 6 nuclei per resin molecule.

As pointed out in our aforementioned co-pend- I ing application SerialNo. 8,723, other means are available to yield resins in which there maybe present a larger number of phenolic nuclei, for instance, -7 to 15.Such resins are conveniently obtained by subjecting the resin obtainedin the conventional manner to further treatment under a vacuum at atemperature belowthe pyrolytic point of the resin. Sometimes theexpression "low-stage resin or low-stage intermediate is employed tomeana stage having 6.0r '7 units, or even less. In the appended claimswe have used low-stage to mean 3 to 7 units, based on average molecularweight.

In the examples given we have found that the resin unit is apt tocontain on the average of about 5 nuclei. For convenience, we havearbitrarily introduced either one or two moles of of salicylic acid perresin unit. A larger number, for instance, 3 or 4, could be introduced,particularly if the resin unit were larger, for instance, contained 6 or7 units. Such resins can be prepared at substantially highertemperatures, substituting cymene, tetralin, or some other suitablesolvent which boils at a higher temperature, instead of xylene, andincreasing the amount of catalyst somewhat; for instance, doubling or.tripling the quantity of catalyst. For practical purposes, ourpreference is a resin having approximately 4 to 5 phenolic units perresin molecule, with 1 or 2 of such units being contributed by thesalicylic acid radical.

Summarizing what has been said previously, it will be noted thatrtheseresins are low-stage resins, i. e., have 7 aromatic nuclei, or less, andthat there is always a plurality of alkylated phenol nuclei, incomparison with the salicylic acid nuclei, and preferably not more thanone unit is contributed by salicylic acid in achain of a total of about4 or 5 units. Needless to say, if one mixes one, part of salicylic acidwith three parts, four parts, or 3% parts of an alkylated phenol, andproduces a resin, one does not necessarily obtain a 4-unit, 5-unit, or4- and 5-unit half-and-half mixture; but there are produced some 3-unitresin chains, some 4, some 5, some 6, and possibly a few 7-unit chains.The length of chain is, of course, based on molecular weightdeterminations, using either the freezing point depression, or boilingpoint rise. Such basis, of course, must be a statistical average forreasons just noted. The outstanding type of resin is the oil-solubleresin having a total length equivalent to 4-to-6 phenolic nuclei'ofwhich one, and only one, is salicylic acid.

PART 2- We have previously pointed out that the manufacture of theseresins is similar to that employed in manufacturing resins from analkylated In any event, the selec-..

, playing a reflux condenser.

phenol alone, as distinguished from a mixture of salicylic acid or itsequivalent, and an alkylated phenol. We have pointed out also therelation-.

ship between such procedure and th manufac- Example 1b The resinemployed was the acid-catalyzed paratertiary butylphenol-formaldehyderesin of Example 1a. (Such resin can be purchased in the open market.)The resin was powdered and 'mixed with an equal weight of xylene, so asto obtain solution by means of a stirring device em- 170 grams of theWhat is resin were dissolved in or mixed with 170 grams of xylene. Tothe mixture there was added 1.7 grams of sodium methylat powder. Thesolutlon or suspension was placed in an autoclave and approximately 400grams of ethylene oxide by weight were added in 6 portions ofapproximately 65 to 75 grams each. After each portion was added, thereaction was permitted to take place for approximately 4 hours. Thetemperature employed was approximately 150 to 165 C. and a maximum gaugepressure of approximately 150 pounds per square inch. The minimum gaugepressure is approximately 20 pounds per square inch. At the end of each4-hour period there is no further drop in pressure, thus indicating thatall the ethylene oxide present has reacted and the pressure registeredon the gauge represents the vapor pressure of xylene at the indicatedtemperature. After the sixth and final portion of ethylene oxide hasbeen added, a test is made on the resultant. I

In one such operation, the resultant, when cold, was a viscous, opaqueliquid, emulsifiable in water even'in presence of the added xylene. Thisindicated that incipient emulsification, in absence of xylene, probablyappeared at the completion'of the fourth addition of ethylene oxide. Inother words, 150 grams or 1'75 grams of ethylene oxide are suflicient togive incipient hydrophile properties in absence of xylene. The initialpoint approximates ethylene oxide equal to slightly less than 100% ofthe weight of the initial resin. .In this instance, in order to obtaingreater solubility, the amount of ethylene oxide' in which the ratio ofethylene oxide to resin is about 2: 1. A compound of this constitution,containing a small amount of xylene, was light amber in color, misciblewith water and had a viscosity resembling that of castor oil.

Example 2b 1 The same reactants, and procedure were employedas inExample 1b, preceding, except that propylene oxide was employed insteadof ethylene oxide. The resultant, even on the addition of the alkyleneoxide in the weight proportions of the previous example, has'diminishdhydra: phile properties, in comparison with the resultants of Example1b. This illustrates the point that propylene oxide and butylene oxidegive products of lower levels of hydrophile properties than doesethylene oxide.

Example 3b I The same reactants and procedure were followed as inExample 112, except thatone mole of glycide was employed initially perhydroxyl radical. This particular reaction was conducted with extremecare and the glycide was added in small amounts representing fractionsof a mole.

Ethylene oxide was then added, following the procedure of Example 11),to produce products of greater hydrophile properties. We are extremelyhesitant tosuggest even the experimental use of glycide andmethylglycide, for the reason that disastrous results may be obtainedeven in ex-- perimentation with laboratory quantities.

Example 4b The 'resin employed was the one described under the headingof Example 2a, preceding. The amount of resin solution employed was 200grams. This solution contained 50% by weight of solvent. .Sodiummethylate equivalent to 2% by'wei'ght based on the resin was emloyed asa During the first addition ethylene oxide the maximum temperature loyedwas 124 C. The maximum gauge pressure-was 175 pounds per square inch.The amount of ethylene oxide added was grams. The time required was 2hours. The product at'the end of this time was substantially insoluble.The equipment employed was the same as that described in previousexamples, such as Example 1b. This last statement applies to allsubsequent examples, ofv

course, also. and also to the further additions of an alkylene oxide inthe instant example.

In the second addition of ethylene oxide the maximum temperatureemployed was C., the i maximum pressure 125 pounds, the amount ofethylene oxide added was 100 grams, and the time required for additionwas 3 hours. The product at the end of this period waswateremulsitlable.

During the third addition of ethylene oxide the maximum temperature was146 C., the maximum gauge pressure pounds, the amount of ethylene oxideadded 100 grams, and the time required 2 hours. At the end of this timethe product was almost water-soluble.

In the fourth addition of ethylene oxide the maximum temperatureemployed was 162 C., the I maximum pressure 105 pounds, the amount ofethylene oxide added 100 grams, and the time required to make theaddition was 3 hours.

The product at theend of this time was completely soluble in water andno further addition of ethylene oxide was made.

Example 5b The resin used was the one described under the heading ofExample 3a. The amount of resin solution employed was 200 grams. Thissolution maximum pressure was 95 pounds, the amount of ethylene oxideadded was 100 grams, the time required was 4 hours, and the product atthe,

end of this time was water-emulsifiable. In the second addition ofethylene oxide the maximum 17 temperature was 94 0., and the maximumpressure 120 pounds. The amount of ethylene oxide added. was 100 grams,and the time required to add it was three fourths of an hour. Theproduct at the end of this period was emulsifiable.

In the third addition of ethylene oxide the maximum temperature was 120C., themaximum pressure 55 pounds, and the amount of ethylene oxideadded was 100 grams. The time required was 2 hours. The product at theend of this time was becoming water-soluble.

In the fourth addition of ethylene oxide the maximum temperature was 134C., the maximum pressure 80 pounds, the amount of ethylene oxide 100grams, and the time required to add the oxide was 2 hours. At the end ofthis addition the product was becoming more soluble.

In the fifth addition of ethylene oxide the maximum temperature was 134C., the pressure was 120 pounds, and the amount of ethylene oxide addedwas 100 grams. The time required to add the ethylene oxide was 2 hours.The product was still becoming more soluble,-

In the sixth addition of ethylene oxide the maximum temperature was 150C., the maximum pressure 110 pounds, the amount added was 100 grams, andthe time required to add the oxide was 2 hours. At the end of this stagethe product was almost water-soluble. in fact, the solubility was morethan ample for use as a demrlsifier, and further addition of oxide wasstopped.

Example 6b The final product obtained by use of ethylene oxide inExample 117, preceding, was treated further with propylene oxide. To thefinal product so obtained in Example 1b, preceding, there was added anadditional 1/; grams of sodium methylate and then 100 grams of propyleneoxide, The autoclave was sealed and operated in the same manner as inExample 1a. The addition of propylene oxide, notwithstanding the addedcatalyst, was rather slow. The time required to add the propylene oxidewas 5 hours at a maximum temperature of 165 C., and a maximum gaugepressure of 150 pounds. The solubility at the end of this period wassubstantially the same as before, i. e., the final addition of thisamount of propylene oxide did not markedly change the solubilitycharacteristics of the resin. This same procedure can, of course, beemployed in connection with subsequent examples, such as 7b to 24b,inclusive.

For convenience of comparison, as well as for purpose of brevity, etc.,the next series of compounds are presented in tabular form, as follows:

Wt. of Wt. of Ex No Ex. No. Resin Solvent Solvent Catalyst of Resin80111. Free Added (N aOMe) Used Resin Grams Gm ms Grams Grams 9b 9a Z10106. 93. 5 3 b 1011 200 107. 0 93. 0 3 11b 11a 300 110. 0 190. 0 3 12b120. 300 77. 6 22. 4 3 13b 13 300 92. 0 208. 0 3 14b 1441 300 88. 5 211.5 4 15b 1511. 300 112. 0 188. 0 4 16b 160 300 115. 5 184. 5 4 17b 1711300 80. 6 219. 4 4 18b 1841 300 117. 5 182. 5 4 19b 1911 300 117. 5 182.5 10 mb 200 300 114. 6 185. 4 4 21b 2111 300 114. 6 185. 4 4 22b 22a 300125. 0 175. 0 4 23b 2311 300 128. 8 171. 2 4 24b 24m 300 127. 0 173. 0 4

FIRST OXYETHYLATION STEP Mex. Time Ex. No. ETD Temp., re- SolubilityAdded 0 0 lbs.

- 8min quired Grams Home 155 195 5% Water-emulsiflable. 162 170 5% D0.150 185 2 Do. 130 162 220 6 DO. 130 155 175 5% D0. 120 165 180 5 D0. 120165 180 5 Do. 127 162 175 3 D0. 127 162 165 5 D0. 110 158 160 3 D0. 110155 3 Do. 107 160 170 5% D0. 116 155 180 5 Do. 121 162 180 5% D0. 121152 190 4% D0. 106 160 170 6 D0. 100 160 175 6 Do. 103 165 175 5% D0.

SECOND OXYETHYLATION STEP Max. Max. Time EIO Press. Ex. No. Temp., re-Solubility Added 0., gfii quired Grams Hours 100 210 7 Water-soluble.100 156 180 2% Water-emulsiiiable,

semi-rubbery. 100 160 190 5 Water-emulsifiable. 100 158 170 5% Do. 100160 216 6 D0. 100 163 180 6 D0. 100 163 180 6 D0. 100 160 170 5 Do. 100172 I 5% Almost soluble. 100 180 5% Water-emulsiflable. 100 155 4%Almost water-soluble. 100 150 175 5 Water-emulsiflable. 100 165 5% Do.100 158 170 6 Do. 100 150 160 6 D0. 100 160 210 5% D0. 100 160 215 5%D0. 100 165 5% Do.

THIRD OXYETHYLATION STEP Max Max. Time ETO Press Ex. No. Temp., re-Solubility 0., gi quired Grams Hours 100 160 190 11 Water-emulsiflable.100 155 155 3 D0. 100 158 220 6 Rubberlike, almost water-soluble. 100160 218 6 Almost water-soluble. 100 162 175 5% Water-soluble. 100 162175 5% D0. 100 155 5% D0. 100 160 170 5% D0. 100 160 160 5 Do. 100 155170 5 Do. 100 158 210 5% Water-emulsiflable. 100 160 180 4%Water-soluble. 100 160 215 5% D0. 100 155 202 5% D0. 100 160 205 7 D0.100 160 210 7 Do. 100 158 195 6 D0.

Max Max. Time Ex.No. Egig Temp., gg re- Solubility 0., Sq h quired Hours155 180 11 Water-soluble. 150 175 4% Water-soluble; almost rubberlike.157 205 6 Water-soluble. 165 175 5% Do. 7 160 6% Water-emulsiflable; 165190 4 Do.

FIFTH OXYETHYLATION STEP Max Max Time ETO Press. Tem re- Remarks Ex' hoAdded C? h quired Home 86 mm 100 g. carbitol added after 2nd ETO step.96 100 g. carbitol added after 4th ETO step. 100 100 g. carbitol addedafter 3rd El 0 step. 110 Somewhat viscous,

tendency to string. 12!) N on-viscous liquid. 130-----. Do. 14!) Do.15!) Do. 160 Do. 17b Do. 18!) ,.Do. 190 Do. 200 Do. 215 Do. 2% I 155 198W N01? giscous liquid 100 4 23b almost water-soluble. 24b Non-viscousliquid.

Attention is directed to the fact that the resins herein described mustbe fusible and soluble in a non-polar solvent, such as xylene, althoughobviously, they may be soluble and usually are, in other polar oroxygenated solvents, as previously noted. Fusible resins invariably aresoluble in one or more organic solvents, such .as those mentionedelsewhere herein. It is to be emphasized, however, that the organicsolvent employed to indicate or assure that the resin meets thisrequirement, need not be the one used in oxyalkylation. Indeed, solventswhich are susceptible to oxyalkylation are included in this group oforganic solvents. Examples of such solvents are alcohols andalcohol-ethers. However, where a resin is soluble in an organic solvent,there are usually available other organic solvents which are notsusceptible to oxyalkylation, useful for the oxyalkylation step. In anyevent, the organic solvent-soluble resin can be finely powdered, forinstance, to 100 to 200 mesh, and a slurry or suspension prepared inxylene or the like, and subjected to oxyalkylation. The fact that theresin is soluble in an organic solvent, or the fact that it is fusible,means that it consists of separate molecules. Phenolaldehyde resins ofthe type herein specified possess reactive hydroxyl groups and areoxyalkylation-susceptible. Over and above this the peculiar resinsherein described, of course, contain a carboxyl radical which makes themavailable for a variety of reactants, as previously indicated.

Considerable of what is said immediately hereinafter is concerned withthe ability to vary the hydrophile properties of the compounds used inthe process from minimum hydrophile properties to maximum hydrophileproperties. Even more remarkable and equally diillcult to explain, arethe versatility and utility of these compounds as one goes from minimumhydrophile property to ultimate maximum hydrophile property. Forinstance, minimum hydrophile property may be described roughly as thepoint where two ethyleneoxy radicals or moderately in excess thereof areintroduced per phenolic hydroxyl. Such minimum hydrophile property orsub-surface-activity or minimum surface-activity means that the productshows at least; emulsifying properties or self-dispersion in cold oreven in warm distilled water (15 to 40 C.) in concentrations of 0.5% to5.0%. These materials are generally more soluble in cold water than warmwater, and may even be very insoluble in boiling water. Moderatelyhightemperatures aid in reducing the viacosity of the solute underexamination. Sometimes if one continues to shake a hot solution, eventhough cloudy or containing an insoluble phase, one finds that solutiontakes place to give a homogeneous phase as the mixture cools. Suchself-dispersion tests are conducted in the absence of an insolublesolvent.

When the hydrophile-hydrophobe balance is above the indicated minimum (2moles of ethylene oxide per phenolic nucleus or the equivalent) butinsufllcient to give a sol as described immediately preceding, then, andin that event hydrophile properties are indicated by the iact'that onecan produce an emulsion by having present 10% to 50% 01' an inertsolvent such as xylene. All that one need to do is to have a xylenesolution within vigorously so as to obtain an emulsion which;

may be of the oil-in-water type or the water-inoil type (usually theformer) but, in any event, I

is due to the hydrophile-hydrophobe balance of the oxyalkylatedderivative. We prefer simply to use the xylene diluted derivatives,which are described elsewhere, for this test rather than evaporate thesolvent and employ any more elaborate tests, it the solubility is notsufllcient to permit the simple sol test in water previously noted.

If the product is not readily water soluble it may. be dissolved inethyl or methyl alcohol, ethylene glycol diethylether, or diethyleneglycol diethylether, with a little acetone added it required, making arather concentrated solution, for instance 40% to 50%, and then addingenough of the concentrated alcoholic or equivalent solution to give thepreviously suggested 0.5 to 5.0%

strength solution. If the product is self-dispersing (i. e., if theoxyalkylated product; is a liquid or a liquid solutionseli-emulsiilable) such sci or dispersion is referred to as at leastsemi-stable in the sense that sols, emulsions, or dispersions preparedare relatively stable, if they remain at least for some period of time,for instance 30 minutes to two hours, before showing any markedseparation. Such tests are conducted at room temperature 22 (3.).Needless to say, a test can be made in presence of an insoluble solventsuch as 5% to 15% 01' xylene, as noted in previous examples. If suchmixture, i. e., containing a water-insoluble solvent, is at leastsemi-stable, obviously the solvent-free product would be even more so.Surface-activity representing an advanced hydrophile-hydrophobe balancecan also be determined by the use of conventional measurementshereinafter described. One outstanding characteristic propertyindicating surfaceactivity in a material is the ability to form apermanent foam in dilute aqueous solution, for example, less than 0.5%,when in the higher oxyalkylated stage, and to form an emulsion inmixture of compounds into products which are distinctly hydrophile. atleast to the extent that -markedly enhanced hydrophile propertiesoverand above the initial stage of self -emulsiflability, although we havefound that with products of the type used herein, most efficaciousresults are obtained with products which do not have hydrophileproperties beyond the stage of self-dispersibility.

More highly oxyalkylated resins give colloidal solutions or sols whichshow typical properties comparable to ordinary surface-active agents.Such conventional surface-activity may be measured by determining thesurface tension and the interfacial tension against paraffin oilor thelike. At the initial and lower stages of oxyalkylation, surface-activityis not suitably determined in this same manner but one may employ anemulsification test. Emulsions come into existence as a rule through thepresence of a surface-active emulsifying agent. Some surface-activeemulsifying agents such as mahogany soap may produce a water-in-oilemulsion or an oil-in-water emulsion depending upon the ratio of the twophases, degree of agitation, concentration of emulsifying agent, etc.

The same is true in regard to the oxyalkylated resins herein specified,particularly in the lower stage of oxyalkylation, the so-calledsub-surface-active stage. The surface-active properties are readilydemonstrated by producing a xylenewater emulsion. A suitable procedureis as follows: The oxyalkylatediresin is dissolved in an equal weight ofxylene. Such 50-50 solution is then mixed with 13 volumes of water andshaken to produce an emulsion. The amount of xylene is invariablysuflicient to reduce even a tacky resinous product to a solution whichis readily dispersible. The emulsions so produced are usuallyxylene-in-water emulsions (oil-in-water type) particularly when theamount of distilled water used is at least slightly in excess of thevolume of xylene solution and also if shaken vigorously. At times,particularly in the lowest stage of oxyalkylation, one may obtain' awaterin-xylene emulsion (water-in-oil type) which is apt to reverse onmore vigorous shaking and further dilution with water.

If in doubt as to this property, comparison with a resin Obtained frompara-tertiary butylphenol and formaldehyde (ratio 1 part phenol to 1.1formaldehyde) using an acid catalyst and then followed by oxyalkylationusing 2 moles of ethylene oxide for each phenolic hydroxyl, is helpful.a molecular weight indicating about 4 units per resin molecule. Suchresin, when diluted with an equal weight of xylene, will serve toillustrate the above emulsification test.

In many cases, there is no doubt as to the presence or absence ofhydrophile or surfaceactive characteristics in the products used inaccordance with this invention. They dissolve or disperse in water; andsuch dispersions foam readily. With borderline cases, i. e., those whichshow only incipient hydrophile or surface-active property(sub-surface-activity) tests for emulsifying properties orself-dispersibility are useful. The fact that a reagent is capable ofproducing a. dispersion in water is proof that it is distinctlyhydrophile. In doubtful cases, comparison can Such resin prior tooxyalkylation has be made with the 22 butylphenol formaldehyde resinanalog wherein 2 moles of ethylene oxide have been introduced for eachphenolic nucleus.

The presence of xylene or an equivalent waterinsoluble solvent may maskthe point at which resultant may show initial or incipient hydrophileproperties, whereas in presence of xylene such properties would not benoted. In other cases, the first objective indication of hydrophileproperties may be the capacity of the material to emulsify an insolublesolvent such as Xylene. It is to be emphasized that hydrophileproperties herein referred to are such as those exhibited by incipientself-emulsification or the presence of emulsifying properties and gothrough the range of homogeneous dispersibility or admixture with watereven in presence of added water-insoluble solvent and minor proportionsof common electrolytes as occur in oil field brines.

Elsewhere, it is pointed out that an emulsiflcation test may be used todetermine ranges of surface-activity and that such emulsification testsemploy a xylene solution. Stated another way, it is really immaterialwhether a xylene solution produces a sol or whether it merely producesan emulsion.

In light of what has been'said previously in regard to the variation ofrange of hydrophile properties, and also in light of what has been saidas to the variation in the effectiveness of various alkylene oxides, andmost particularly of all ethylene oxide, to introduce hydrophilecharacter. it becomes obvious that there is a wide variation in theamount of alkylene oxide employed, as long as it is at least 2 moles perphenolic nucleus, for producing products useful for the practice of thisinvention. Another variation is the molecular size of the resin chainresulting from reaction between the difunctional phenol and the aldehydesuch. as formaldehyde. It is well known that the size and nature orstructure of the resin polymer obtained varies somewhat with theconditions of reaction, the proportions of reactants, the nature of thecatalyst, etc.

PART 3 Conventional demulsifying agents employed in the treatment of oilfield emulsions are used as such, or after dilution with any suitablesolvent, such as water, petroleum hydrocarbons, such as benzene,toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols,particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol,denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octylalcohol, etc., may be employed as diluents. Miscellaneous solvents, suchas pine oil, carbon tetrachloride, sulfur dioxide extract obtained inthe refining of petroleum, etc., may be employed as the demulsifyin'gagent of our process may be admixed with one or more of the solventscustomarily used in connection with conventional demulsifying agents.Moreover, said material or materials may be used alone or in admixturewith other suitable well-known classes of demulsifying agents.

It is well known that conventional demulsifying agents may be used in awater-soluble form, or in an oil-soluble form, or in a form exhibitingboth 011- and water-solubility. Sometimes they may be used in a formwhich exhibits relatively limited oil-solubility. However, since suchreagents are frequently used in a ratio of 1 to 10,000, or 1 to 20,000,or 1 to 30,000, or even 1 to 40,000, or 1 to 50,000, as in desaltingpractice, such an apparent insolubility in oil and water is notsigniflcant, because said reagents undoubtedly have solubility withinsuch concentrations. This same fact is true in regard to the material ormaterials employed as the demulsifying agent of our process.

In practising our process for resolving petroleum emulsions of thewater-in-oil type, a treat? ing agent or demulsifying agent of the kindabove described is brought into contact with or caused to act upon theemulsion to be treated, in any of the various apparatus now generallyused to resolve or break petroleum emulsions with a chemical reagent,the above procedure being used alone or in combination with otherdemulsifying procedure, such as the electrical dehydration process.

One type of procedure is to accumulate a volume of emulsified oil in atank and conduct a batch treatment type of demulsification procedure torecover clean oil. In this procedure the emulsion is admixed with thedemulsifier, for example by agitating the tank of emulsion and slowlydripping demulsifier into the emulsion. In some cases mixing is achievedby heating the emulsion while dripping in the demulsifier, dependingupon the convection currents in the emulsion to produce satisfactoryadmixture. In a third modification of this type of treatment, acirculating pump withdraws emulsion from, e. g., the bottom of the tank,and re-introduces it into the top of the tank, the demulsifier beingadded, for example, at the suction side of said circulating pump.

In a second type of treating procedure, the demulsifier is introducedinto the well fluids at the well-head or at some point between thewell-head and the final oil storage tank, by means of an adjustableproportioning mechanism or proportioning pump. Ordinarily the flow offluids through the subsequent lines and fittings suflices to produce thedesired degree of mixing of demulsifier and emulsion, although in someinstances additional mixing devices may be introduced into the flowsystem. In thi general procedure, the system may include variousmechanical devices for withdrawing free water, separating entrainedwater, or accomplishing quiescent settling of the chemicalized emulsion.Heating devices may likewise be incorporated in any of the treatingprocedures described herein.

A third type of application (down-the-hole) of demulsifier to emulsionis to introduce the demulsifier either periodically or continuously indiluted or undiluted form into the well and to allow it to come to thesurface with the well fluids, and then to flow the chemicalized emulsionthrough any desirable surface equipment, such as employed in the othertreating procedures. This particular type of application is decidedlyuseful when the demulsifier is used in connection'with acidification ofcalcareous oilbearing strata, especially if suspended in or dissolved inthe acid employed for acidification.

In all cases, it will be apparent from the loregoing description, thebroad process consists simply in introducing a relatively smallproportion of demulsifier into a relatively large proportion ofemulsion, admixing the chemical and emulsion either through natural flowor through special apparatus, with or without the application of heat,and allowing the mixture to stand quiescent until the undesirable watercontent of the emulsion separates and settles from the mass.

The following is a typical installation:

A reservoir to hold the demulsifier of the kind described (diluted orundiluted) is placed at the well-head where the efliuent liquids leavethe well. This reservoir or container, which may vary from 5 gallons to50 gallons for convenience, is connected to a proportioning pump whichinjects the demulsifier drop-wise into the fluids leaving the well. Suchchemicalized fluids pass through the flowline into a settling tank. Thesettling tank consists or a tank 01 any convenient size, for instance,one which will hold amounts of fluid produced in 4 to 24 hours (500barrels to 2000 barrels capacity), and in which there is a perpendicularconduit from the top of the tank to almost the very bottom so as topermit the incoming fluids to pass from the top or the settlingtank tothe bottom, so that such incoming fluids do not disturb stratificationwhich takes place during the course of demulsification. The

settling tank has two outlets, one being below the water level to drainofl the water resulting from demulsification or accompanying theemulsion as free water, the other being an oil outlet at the toptopermit the passage of dehydrated oil to a second tank, being a storagetank, which holds pipeline or dehydrated oil. If desired, the

conduit or pipe which serves to carry the fluids from the well to thesettling tank may include a section of pipe with baffles to serve as amixer, to insure thorough distribution of the demulsifler throughout thefluids, or a heater for raising the temperature of the fluids to someconvenient temperature, for instance, to F., or both heater and mixer.

Demulsification procedure is started by simply setting the pump so as tofeed a comparatively large ratio of demulsifier, for instance, 1:5,000.As soon as a complete break or satisfactory demulsiflcation is obtained,the pump is regulated until experience shows that the amount ofdemulsifier being added is just suflicient to produce clean ordehydrated oil. The amount being fed at such stage is usually 1:10,000,1:15,000, 1:20,000, or the like.

In many instances the oxyalkylated products.

herein specified as demulsiflers can be conveniently used withoutdilution. However, as previously noted, they may be diluted as desiredwith any suitable solvent. For instance-by mixing '75 parts by weight ofan oxyalkylated derivative with 15 parts by weight of xylene and 10parts by weight of isopropyl alcohol, an excellent de- The followingmixture illustrates of oxyalkylene groups to phenolic nuclei is at least2:1 and the alkylene radicals of the oxyalkylene groups are selectedfrom the class consisting of ethylene, propylene, butylene, hydroxypropylene and hydroxybutylene radicals; said phenol being a mixture of2,4,6 04- to C14- hydrocarbon-substituted monocyclic monohydric .phenoland salicylic acid, the amount of salicylic acid employed in relation tothe hydrocarbonsubstituted phenol being suflicient to contribute atleast one salicylic radical per resin molecule; and with the finalproviso that the hydrophile properties of said oxyalkylated resin in anequal weight of xylene are suflicient to produce 26 final proviso thatthe hydrophile properties of said oxyalkylated resin in an equal weightof xylene are sufficient to produce an emulsion when said xylenesolution is shaken vigorously one to three volumes of water.

3. A process for breaking petroleum emulsions with 'of the water-in-oiltype, characterized by subjecting the emulsion to the action of ademulsifier including hydrophile hydroxylated synthetic products; saidhydrophile synthetic products being oxyalkylation products of (A) Analpha-beta alkylene oxidehavlng not more than 4 carbon atoms andselected from the class consisting of ethylene oxide, propylene oxide,butylene oxide, glycide and methylglycide; and

(B) An oxyalkylation-susceptible, fusible, xy-

lene-soluble, water-insoluble, acid-catalyzed, lowan emulsion when saidxylene solution is shaken vigorously with one to three volumes of water.

2. A process for breaking petroleum emulsions of the water-in-oil type,characterized by subjecting the emulsion to the action of a demulsifierincluding hydrophile hydroxylated synthetic products; said hydrophilesynthetic products being oxyalkylation products of (A) An alpha-betaalkylene oxide having not more than 4 carbon atoms and selected from theclass consistin of ethylene oxide, propylene oxide, butylene oxide,glycide and methylglycide; and

(B) An oxyalkylation-susceptible, fusible, xylene-soluble,water-insoluble, acid-catalyzed, lowstage phenol-aldehyde resin; saidresin being derived by reaction between a mixture of a difunctionalmonohydric hydrocarbon-substituted phenol and salicylic acid on the onehand, and an aldehyde having not over 8 carbon atoms and reactivetowards both components of the mixture on the other hand; the amount ofsalicylic acid employed in relation to the non-carboxylated phenol beingsuflicient to contribute at least one salicylic acid radical per resinmolecule; said resin being formed in the substantial absence oftrifunctional phenols, and said phenol being of the formula:

in which R is a hydrocarbon radical having at least 4 and not more than14 carbon atoms and substituted in the 2,4,6 position; said oxyalkylatedresin being characterized by the introduction into the resin molecule ofa plurality of divalent radicals having the formula (R1O)1v in which R1is a member selected from the class consisting of ethylene radicals,propylene radicals, butylene radicals, hydroxypropylene radicals, andhydroxybutylene radicals, and n is a numeral varying from 1 to 30, withth proviso that at least 2 moles of alkylene oxide be introduced foreach phenolic nucleus; and with the stage phenol-aldehyde resin; saidresin being derived by reaction between a mixture of a difunctionalmonohydric hydrocarbon-substituted phenol and salicylic acid on the onehand, and an aliphatic aldehyde having not over 8 carbon atoms andreactive towards both components of the mixture on the other hand; theamount of salicylic acid employed in relation to the noncarboxylatedphenol being suflicient to contribute at least one salicylic acidradical per resin molecule; said resin being formed in the substantialabsence of trifunctional phenols, and said phenol being of the formula:

in which R is a hydrocarbon radical havin at least 4 and not more than14 carbon atoms and substituted in the 2,4,6 position; said oxyalkylatedresin being characterized by the introduction into the resin molecule ofa plurality of divalent radicals having the formula (R1O)1u in which R1is a member selected from the class with one to three volumes of water.

4. A process for breaking petroleum emulsions of the water-in-oil type,characterized by subjecting the emulsion to the action 'of a demulsifierincluding hydrophile hydroxylated synthetic products; said hydrophilesynthetic products being oxyalkylation products of (A) An alpha-betaalkylene oxide having not more than 4 carbon atoms and selected from theclass consisting of ethylene oxide, propylene oxide, butylene oxide,glycide and methylglycide; and i (B) An oxyalkylation-susceptible,fusible, xylene-soluble, water-insoluble, acid-catalyzed lowstage,phenol-aldehyde resin; said resin being derived by reaction between amixture of difunctional monohydric hydrocarbon-substituted phenol andsalicylic acid on the one hand, and an aliphatic aldehyde having notover 8 carbon atoms and reactive towards both components of the mixtureon the other 27 hand; the amount otsalicylic acid employed in relationto the non-carboxylated phenol being sufficient to contribute at inwhich R is a hydrocarbon radical having at least 4 and not more than 14carbon atoms and substituted in the 2,4,6 position; said oxyalkylatedresin being characterized by the introduction into the resin molecule ofa plurality of divalentradicals having the formula (R1O)n' in which R1is a member selected from the class consisting of ethylene radicals,propylene radicals, butylene radicals, hydroxypropylene radicals, andhydroxybutylene radicals, and n is a numeral varying from 1 to 30, withthe proviso that at least 2 moles of alkylene oxide be introduced foreach phenolic nucleus; and with the further proviso that the hydrophileproperties of said oxyalkylated resin in an equal weight of xylene aresumcient to produce an emulsion when said xylene solution is shakenvigorously with one to three volumes of water; and with the finalproviso that the number 01 salicylic acid nuclei per resin molecule benot greater than 2.

5. A process for breaking petroleum emulsions of the water-in-oil type,characterized by subjecting the emulsion to the action of a demulsiflerinculding hydrophile hydroxylated synthetic products; said hydrophilesynthetic products being oxyalkylation products of (A) An alpha-betaalkylene oxide having not more than 4 carbon atoms and selected from theclass consisting of ethylene oxide, propylene oxide, butylene oxide,glycide and methylglycide; and

(B) An oxyalkylation-susceptible, fusible, xylene-soluble,water-insoluble, acid-catalyzed, lowstage, phenol-aldehyde resin; saidresin being derived by reaction between a mixture of a difunctionalmonohydric hydrocarbon-substituted phenol and salicylic acid on the onehand, and an aliphatic aldehyde having not over 8 carbon atoms andreactive towards both components of the mixture on the other hand; theamount of salicylic acid employed in relation to the non-carboxylatedphenol being suilicient to contribute at least one salicylic acidradical per resin molecule; said resin being formed in the substantialabsence of trifunctional phenols; and said phenol being 01' the formula:

- of divalent radicals having the formula (R10)n' ,in which R1 is amember selected from the class consisting of ethylene radicals,propylene radicals, butylene radicals, hydroxypropylene radicals, andhydroxybutylene radicals, and n is a numeral varying from 1 to 30, withthe proviso that at least 1 2 moles of alkylene oxide be introduced foreach phenolic nucleus; and with the further proviso that the hydrophileproperties or said oxyale' kylated 'resin in an equal weight of xyleneare suflicient to produce an emulsion when said xylene solution isshaken vigorously with one to three volumes of water; and with theflnal'pro' viso that the number of salicylic acid nuclei per resinmolecule be not greater than 2.

6. A process for breaking petroleum emulsions of the water-in-oil type,characterized by subjecting'the emulsion to the action of a demulsiflerincluding hydrophile hydroxylated synthetic products; said hydrophilesynthetic products be ing oxyethylation products of (A) Ethylene oxide;and

(B) An oxyalkylation-su'sceptible, fusible, iw

lene-soluble, water-insoluble, acid-catalyzed, lowstage phenol-aldehyderesin; said resin being lie-- rived by reaction between a mixture of adifunc tional monohydric hydrocarbon-substituted phenol and salicylic,acid on the one hand, and an aliphatic aldehyde having not over 8 carbonatoms and reactive towards both components of the mixture on the otherhand; the amount of salicylic acid employed in relation to thenon-carboxylated phenol being sufllcient to contribute at least onesalicylic acid radical per resin molecule; said resin being formed inthe substantial absence of trii'unctional phenols; said phenol being ofthe formula: 7

in which R'is a hydrocarbon radical having at least 4 and not more than14 carbon atoms; said orwalkylated resin being characterized by theintroduction into the resin molecule of a plurality of divalent radicalshaving the formula (R10) 1-.

in which'Ri is a member selected from the class consisting of ethyleneradicals, propylene radicals, butylene radicals, hydroxypropyleneradicals, and hydroxybutylene radicals, and n is a. numeral varying from1 to 30, with the proviso that at least 2 moles of alkylene oxide beintroduced for each phenolic nucleus; and with the iurther-proviso thatthe hydrophile properties of said oxyalkylated resin in an equal weightof xylene are suifljecting the emulsion to the action of a demulsifierincluding hydrophilehydroxylated synthetic products; said hydrophilesynthetic products being' oxyethylation products of (A) Ethylene oxide;and (B) An oxyalkylaticn-susceptible, fusible, .xylene-soluble,water-insoluble, acid-catalyzed, lowstage, phenol-aldehyde resin; saidresin being de-" rived by reaction between a mixture of a difunctional,monohydric, hydrocarbon-substituted phenol and salicylic acid on the onehand, and an aliphatic aldehyde having not over 8 carbon atoms andreactive towards both components of the mixture on the other hand; theamount of salicylic acid employed in relation to the non-carboxylatedphenol suflicient resin molecule be not greater than 2.

salicylic acid radical per resin molecular said resin being formed inthe substantial absence oi trifunctional phenols; said phenol being ofthe formula:

in which R1 is a member selected from the class consisting of ethyleneradicals, propylene radicals, butylene radicals, hydroxypropyleneradicals, and

hydroxybutylene radicals, and n is a numeral varying from 1 to 30, withthe proviso that at least 2 moles of alkylene oxide be introduced foreach phenolic nucleus; and with the further proviso that the hydrophileproperties of said oxyallwlated resin in an equal weight of xylene aresufllcient to produce an emulsion when said xylene solution is shakenvigorously with one to three volumes of ,water; and with the final pro-'viso that the number of salicylic acidnuclei per 8. A process forbreaking, petroleum emulsions of the water-in-oil type, characterized bysubjecting the emulsion to the action 01' a demulsifler includinghydrophile hydroxylated thetic products; said hydrophilesynthetic prod-'ucts being oxyethylation products of (A) Ethylene oxide; and

(B) An oxyalkylation-susceptible, fusible,

xylene-soluble, water-insoluble, acid-catalyzed. low-stage,phenolealdehyde resin; said resin being derived by reaction between amixture of a ditunctional, monohydric,', hydrocarbon e substitutedphenol and salicylic "acid on the one hand, and an aliphatic aldehydenot over 8 carbon atoms and reactive towards both components of themixture on' the other hand; the amountot salicylic acid employed inrelation to the non-carboxylated phenol being sumcient to contributejust one salicylic acid radical per resin molecule; said resin beingformed in the subto contribute at least one I 30 .stantial absence oftrifunctional phenols; said phenol being or the formula:

ity of divalent radicals having the formula (R10) n' in which R1 is amember selected from the class consisting of ethylene radicals,propylene radicals, butylene radicals, hydroxypropylene radicals, andhydroxybutylene radicals, and n is a numeral varying from 1 to 30, withthe proviso that at least 2 moles of alkylene oxide be introduced foreach phenolic nucleus; and with the further proviso that the hydrophileproperties of said oxyalkylated resin in an equal weight of xylene aresufficient to produce an emulsion when said xylene solution is shakenvigorously with one to three volumes of water; and with the finalproviso that the number of salicylic acid nuclei per resin molecule benot greater than 2.

9. The process of claim 8, wherein the aldehyde is formaldehyde.

10. The process of claim 8, wherein the aldehyde is formaldehyde and thephenol is tertiary amylphenol.

11. The process 01' claim 8, wherein the aldehyde is formaldehyde andthe phenol is tertiary butylphenol.

j 12*. The process of claim 8, wherein the aldehyde is formaldehyde andthe phenol is tertiary nonylphenol.

MELVIN DE GROOTE. BERNHARD KEISER.

REFERENCES CITED The following references are of record in the 45 fileof this patent:

UNITED STATES PATENTS

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE,CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIERINCLUDING A HYDROPHILE OXYALKYLATED PHENOL -C1- TO C8- ALDEHYDE RESIN INWHICH THE RATIO OF OXYALKYLENE GROUPS TO PHENOLIC NUCLEI IS AT LEAST 2:1AND THE ALKYLENE RADICALS OF THE OXYALKYLENE GROUPS ARE SELECTED FROMTHE CLASS CONSISTING OF ETHYLENE, PROPYLENE, BUTYLENE, HYDROXYPROPYLENEAND HYDROXYBUTYLENE RADICALS; SAID PHENOL BEING A MIXTURE OF 2,4,6 C4-TO C14- HYDROCARBON-SUBSTITUTED MONOCYCLIC MONOHYDRIC PHENOL ANDSALICYLIC ACID, THE AMOUNT OF SALICYLIC ACID EMPLOYED IN RELATION TO THEHYDROCARBONSUBSTITUTED PHENOL BEING SUFFICIENT TO CONTRIBUTE AT LEASTONE SALICYLIC RADICAL PER RESIN MOLECULE; AND WITH THE FINAL PROVISOTHAT THE HYDROPHILE PROPERTIES OF SAID OXYALKYLATED RESIN IN AN EQUALWEIGHT OF XYLENE ARE SUFFICIENT TO PRODUCE AN EMULSION WHEN SAID XYLENESOLUTION IS SHAKEN VIGOROUSLY WITH ONE TO THREE VOLUMES OF WATER.